CN114144440B - Single site catalysed multimodal polyethylene composition - Google Patents
Single site catalysed multimodal polyethylene composition Download PDFInfo
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- CN114144440B CN114144440B CN202080052295.0A CN202080052295A CN114144440B CN 114144440 B CN114144440 B CN 114144440B CN 202080052295 A CN202080052295 A CN 202080052295A CN 114144440 B CN114144440 B CN 114144440B
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- Prior art keywords
- ethylene
- polyethylene composition
- butene
- butene copolymer
- copolymer fraction
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- 239000000203 mixture Substances 0.000 title claims abstract description 156
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 109
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 109
- -1 polyethylene Polymers 0.000 title claims abstract description 108
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 136
- 229920001577 copolymer Polymers 0.000 claims abstract description 111
- 239000011347 resin Substances 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000000155 melt Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 56
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 31
- 239000005977 Ethylene Substances 0.000 claims description 31
- 229920001684 low density polyethylene Polymers 0.000 claims description 6
- 239000004702 low-density polyethylene Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000010408 film Substances 0.000 description 98
- 229920000642 polymer Polymers 0.000 description 70
- 239000007789 gas Substances 0.000 description 45
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 28
- 239000002002 slurry Substances 0.000 description 28
- 238000007789 sealing Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 19
- 239000000523 sample Substances 0.000 description 18
- 239000000654 additive Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 238000005243 fluidization Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004364 calculation method Methods 0.000 description 8
- 230000010354 integration Effects 0.000 description 8
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VJLWKQJUUKZXRZ-UHFFFAOYSA-N 2,4,5,5,6,6-hexakis(2-methylpropyl)oxaluminane Chemical compound CC(C)CC1C[Al](CC(C)C)OC(CC(C)C)(CC(C)C)C1(CC(C)C)CC(C)C VJLWKQJUUKZXRZ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CKNXPIUXGGVRME-UHFFFAOYSA-L CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 Chemical compound CCCCC1(C=CC(C)=C1)[Zr](Cl)(Cl)C1(CCCC)C=CC(C)=C1 CKNXPIUXGGVRME-UHFFFAOYSA-L 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The present invention relates to a polyethylene composition comprising a base resin, a process for preparing said polyethylene composition, an article comprising said polyethylene composition and the use of said polyethylene composition for producing an article, wherein the base resin comprises: (A) A first ethylene-1-butene copolymer fraction (A) having a 1-butene content of from 0.5 to 7.5% by weight, based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (A), and a melt flow rate MFR, measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg, in the range of from 1.0 to less than 50.0g/10min 2 The method comprises the steps of carrying out a first treatment on the surface of the And (B) a second ethylene-1-butene copolymer fraction (B) having a higher 1-butene content than the first ethylene-1-butene copolymer fraction; wherein the base resin is polymerized in the presence of a single site catalyst system and has a weight of 913.0 to 920.0kg/m 3 And a 1-butene content of 8.0 to 13.0 wt% based on the total weight of monomer units in the base resin.
Description
Technical Field
The present invention relates to a polyethylene composition comprising two single site catalyzed ethylene-1-butene copolymer fractions having different 1-butene content, a process for preparing said polyethylene composition, an article comprising said polyethylene composition and the use of said polyethylene composition for producing an article.
Background
Polyethylene resins are typically produced in the presence of single site catalysts, such as metallocene catalysts, for flexible packaging applications, such as film applications. Single-site catalyzed polyethylene resins exhibit a unique range of properties in terms of optical and mechanical properties, particularly suitable for film applications.
For example, unimodal polyethylene resins have good properties (e.g., low haze) but exhibit relatively poor melt processing, which can lead to quality problems in the final product.
Multimodal polyethylene resins with two or more different polymer components are better processed, but melt homogenization of multimodal polyethylene can be problematic, leading to non-uniformity of the final product, as evidenced by high gel content of the final product.
WO 00/40620 discloses a process for producing polyethylene compositions in the presence of single site catalysts. WO 99/35652 relates to an insulation composition comprising a crosslinkable multimodal ethylene copolymer obtained by coordination catalyzed polymerization of ethylene and at least one other alpha-olefin. EP 3331950 relates to compatible multi-phase polyamide-polyethylene blends comprising a matrix comprising linear low density polyethylene.
WO 2016/083208 discloses multimodal polyethylene compositions with at least two different comonomers, such as 1-butene and 1-hexene, which exhibit an excellent balance of properties in terms of processability, mechanical properties, sealing properties and optical properties.
In the present invention it has surprisingly been found that polyethylene compositions comprising two ethylene-1-butene copolymers polymerized in the presence of a single site catalyst system, which copolymers differ in terms of 1-butene content and melt flow rate, can achieve a performance balance comparable to multimodal polyethylene compositions of at least two different comonomers of WO 2016/083208.
In general, polyethylene compositions using only 1-butene as comonomer exhibit inferior mechanical properties, especially in terms of tear strength and impact properties, compared to polyethylene compositions additionally comprising 1-hexene comonomer. Furthermore, polyethylene compositions using only 1-butene as a comonomer exhibit inferior optical and heat sealing properties compared to polyethylene compositions additionally comprising 1-hexene comonomer.
In the present invention, it has surprisingly been found that by carefully adjusting the 1-butene content and the melt flow rate of two ethylene-1-butene copolymers, a polyethylene composition having an improved balance of properties in terms of processability, mechanical properties, sealing properties and optical properties can be obtained which is comparable to the properties of polyethylene compositions having at least two different comonomers, such as 1-butene and 1-hexene.
Disclosure of Invention
The present invention relates to a polyethylene composition comprising a base resin, wherein the base resin comprises
(A) A first ethylene-1-butene copolymer fraction (a) having a 1-butene content of 0.5 to 7.5% by weight based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (a) and a melt flow rate MFR measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg in the range of 1.0 to less than 50.0g/10min 2 The method comprises the steps of carrying out a first treatment on the surface of the And
(B) A second ethylene-1-butene copolymer fraction (B) having a higher 1-butene content than the first ethylene-1-butene copolymer fraction;
wherein the base resin is polymerized in the presence of a single site catalyst system and the base resin has a weight of 913.0 to 920.0kg/m 3 And a 1-butene content of 8.0 to 13.0 wt% based on the total weight of monomer units in the base resin.
The invention further relates to a process for preparing a polyethylene composition as defined above or below, comprising the steps of:
a) Polymerizing ethylene and 1-butene monomer in the presence of a single site catalyst system in a first polymerization reactor to form a first polymerization mixture comprising a first ethylene-1-butene copolymer fraction (a) having a 1-butene content of from 0.5 to 7.5% by weight based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (a) and a melt flow rate MFR measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg in the range of from 1.0 to less than 50.0g/10min, and said single site catalyst 2 ；
b) Transferring the first polymerization mixture from the first polymerization reactor to the second polymerization reactor;
c) Polymerizing ethylene and 1-butene monomer in the presence of a single site catalyst in the second polymerization reactor to form a second polymerization mixture comprising the first ethylene-1-butene copolymer fraction (a) and a second ethylene-1-butene copolymer fraction (B);
d) Recovering the second polymerization mixture from the second reactor;
e) Forming a powder having a weight of 913.0 to 920.0kg/m 3 A base resin having a 1-butene content of 8.0 to 13.0% by weight based on the total weight of monomer units in the base resin, and
f) A polyethylene composition was prepared.
Still further, the present invention relates to an article comprising a polyethylene composition as defined above or below.
Furthermore, the present invention relates to the use of a polyethylene composition as defined above or below for the production of an article.
Definition of the definition
The polyethylene composition according to the invention refers to a polymer derived from more than 50 mole% of ethylene monomer units and optionally additional comonomer units.
The term 'copolymer' refers to a polymer derived from ethylene monomer units and additional comonomer units in an amount exceeding 0.05 mole percent.
The polyethylene composition or base resin comprises more than one fraction which differ from each other in at least one property, such as weight average molecular weight or comonomer content, referred to as "multimodal". A multimodal polyethylene composition or base resin is referred to as "bimodal" if it comprises two different fractions and correspondingly as "trimodal" if it comprises three different fractions. The presentation of a plot of the molecular weight distribution curve of such multimodal polyethylene composition or base resin, i.e. the polymer weight fraction as a function of its molecular weight, will show two or more maxima depending on morphology or at least be significantly broadened compared with the curve of the individual fractions.
In the present invention, the two ethylene-1-butene copolymer fractions differ not only in their molecular weight, which may be at their melt flow rate MFR 2 And also differ in their 1-butene content.
The term 'base resin' refers to the polymeric portion of the polyethylene composition that is free of the usual additives for using polyolefins, such as stabilizers (e.g. antioxidants), antacids and/or uv inhibitors, which may be present in the polyethylene composition. Preferably, the total amount of these additives is 1.0% by weight or less of the composition, more preferably 0.5% by weight or less, most preferably 0.25% by weight or less.
Detailed Description
Base resin
The base resin according to the invention comprises two ethylene-1-butene copolymer fractions (A) and (B).
The first ethylene-1-butene copolymer fraction (a) has a 1-butene content of from 0.5 to 7.5 wt%, preferably from 0.6 to 5.0 wt%, still more preferably from 0.7 to 3.5 wt% and most preferably from 0.8 to 3.0 wt%, based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (a).
The first ethylene-1-butene copolymer fraction (A) preferably has a weight of 915kg/m 3 To 955kg/m 3 More preferably 925kg/m 3 To 950kg/m 3 And most preferably 935kg/m 3 To 945kg/m 3 Is a density of (3).
The first ethylene-1-butene copolymer fraction (a) preferably consists of ethylene and 1-butene monomer units.
The first ethylene-1-butene copolymer fraction (A) has a melt flow rate MFR of from 1.0g/10min to less than 50.0g/10min, preferably from 2.0g/10min to 45.0g/10min, still more preferably from 3.0g/10min to 30.0g/10min, even more preferably from 3.5g/10min to 20.0g/10min and most preferably from 4.0g/10min to 10.0g/10min 2 。
It is preferred that the first ethylene-1-butene copolymer fraction (A) has a higher melt flow rate MFR than the second ethylene-1-butene copolymer fraction (B) 2 . It is further preferred that the first ethylene-1-butene copolymer fraction (A) has a higher melt flow rate MFR than the polyethylene composition 2 。
The first ethylene-1-butene copolymer fraction (A) preferably has a melt flow rate MFR of from 60g/10min to less than 150g/10min, preferably from 65g/10min to 140g/10min, still more preferably from 75g/10min to 130g/10min and most preferably from 85g/10min to 120g/10min 21 。
It is preferred that the first ethylene-1-butene copolymer fraction (A) has a higher melt flow rate MFR than the second ethylene-1-butene copolymer fraction (B) 21 . It is further preferred that the first ethylene-1-butene copolymer fraction (A) has a higher melt flow rate MFR than the polyethylene composition 21 。
Higher MFR of the first ethylene-1-butene copolymer fraction (A) compared to the second ethylene-1-butene copolymer fraction (B) and/or the polyethylene composition 2 And/or MFR 21 The value represents a lower molecular weight, such as a lower first ethylene-1-buteneThe weight average molecular weight Mw of the copolymer fraction (A).
Preferably, the first ethylene-1-butene copolymer fraction (a) has a flow rate ratio, i.e. melt flow rate MFR, of from 10 to 25, more preferably from 12 to 22 and most preferably from 15 to 20 21 /MFR 2 Is a ratio of (c).
The first ethylene-1-butene copolymer fraction (a) is preferably present in the base resin in an amount of from 30 to 47 wt%, more preferably from 32 to 46 wt%, and most preferably from 35 to 45 wt%, based on the total weight of the base resin.
The first ethylene-1-butene copolymer fraction (a) is typically polymerized as a first polymer fraction in a multistage polymerization process having two or more polymerization stages in sequence. Thus, the properties of the first ethylene-1-butene copolymer fraction (A) can be directly measured.
The second ethylene-1-butene copolymer fraction (B) preferably has a 1-butene content of from 10.0 to 25.0 wt%, more preferably from 12.5 to 22.0 wt%, still more preferably from 15.0 to 20.0 wt% and most preferably from 16.0 to 18.5 wt%, based on the total weight of monomer units in the second ethylene-1-butene copolymer fraction (B).
The second ethylene-1-butene copolymer fraction (B) preferably has a weight of 870kg/m 3 To 912kg/m 3 More preferably 880kg/m 3 To 910kg/m 3 And most preferably 890kg/m 3 To 905kg/m 3 Is a density of (3).
The second ethylene-1-butene copolymer fraction (B) preferably consists of ethylene and 1-butene monomer units.
The second ethylene-1-butene copolymer fraction (B) preferably has a melt flow rate MFR measured according to ISO 1133 of from 0.05g/10min to less than 1.0g/10min, more preferably from 0.1g/10min to 0.8g/10min, still more preferably from 0.2g/10min to 0.7g/10min and most preferably from 0.3g/10min to 0.6g/10min 2 。
It is further preferred that the second ethylene-1-butene copolymer fraction (B) has a lower melt flow rate MFR than the polyethylene composition 2 。
With first ethylene-1Lower MFR of the second ethylene-1-butene copolymer fraction (B) compared to the butene copolymer fraction (A) and/or the polyethylene composition 2 And/or MFR 21 The values represent higher molecular weights, such as the weight average molecular weight Mw of the higher second ethylene-1-butene copolymer fraction (B).
The second ethylene-1-butene copolymer fraction (B) is typically polymerized as a second polymer fraction in a multistage polymerization process having two or more polymerization stages in sequence in the presence of the first ethylene-1-butene copolymer fraction (a). Therefore, the properties of the second ethylene-1-butene copolymer fraction (B) cannot be directly measured and must be calculated. For calculating comonomer content, density and MFR of the second ethylene-1-butene copolymer fraction (B) 2 Suitable methods for (a) are listed below.
The second ethylene-1-butene copolymer fraction (B) is preferably present in the base resin in an amount of from 43 to 65 wt%, more preferably from 44 to 62 wt% and most preferably from 45 to 60 wt%, based on the total weight of the base resin.
The weight ratio of the first ethylene-1-butene copolymer fraction (a) to the second ethylene-1-butene copolymer fraction (B) in the base resin is preferably from 35:65 to 47:53, more preferably from 37:63 to 46:54 and most preferably from 40:60 to 45:55.
In a preferred embodiment of the present invention, the base resin consists of a first ethylene-1-butene copolymer fraction (A) and a second ethylene-1-butene copolymer fraction (B).
In another embodiment of the invention, the base resin further comprises up to 15 wt%, preferably 2.5 to 15.0 wt%, more preferably 5.0 to 13.0 wt% and most preferably 7.5 to 12.5 wt% of one or more polymers different from the first and second ethylene-1-butene copolymer fractions (a) and (B).
Preferably, the one or more polymers different from the first and second ethylene-1-butene copolymer fractions (a) and (B) are selected from alpha-olefin homo-or copolymers. One particularly suitable polymer that differs from the first and second ethylene-1-butene copolymer fractions (A) and (B) is Low Density Polyethylene (LDPE). Low density polyethylene is a vinyl polymer optionally including other comonomers polymerized in a high pressure process. Such high pressure processes are well known in the art. Optional low density polyethylene is also commercially available.
The base resin of the polyethylene composition of the invention has a 1-butene content of from 8.0 to 13.0 wt%, preferably from 8.3 to 12.0 wt%, still more preferably from 8.5 to 11.5 wt%, even more preferably from 8.7 to 11.0 wt% and most preferably from 9.0 to 11.0 wt%, based on the total weight of monomer units in the base resin.
The base resin of the polyethylene composition of the invention has a weight of 913.0kg/m 3 To 920.0kg/m 3 And preferably 914.0kg/m 3 To 918.0kg/m 3 Is a density of (3).
The base resin preferably has a melt flow rate MFR of 0.7g/10min to 4.0g/10min, preferably 0.9g/10min to 3.0g/10min, still more preferably 1.0g/10min to 2.5g/10min, even more preferably 1.1g/10min to 2.0g/10min and most preferably 1.2g/10min to 1.8g/10min 2 。
The base resin preferably has a melt flow rate MFR of 15g/10min to less than 50g/10min, preferably 17g/10min to 45g/10min, still more preferably 19g/10min to 40g/10min and most preferably 20g/10min to 35g/10min 21 。
Preferably, the base resin has a flow rate ratio FRR of 10 to 30, more preferably 12 to 27 and most preferably 15 to 25 21/5 Melt flow Rate MFR 21 /MFR 2 Is a ratio of (c).
The base resin is preferably present in the polyethylene composition of the invention in an amount of at least 95 wt.%, such as 95.0 wt.% to 100 wt.%, more preferably 99.0 wt.% to 99.95 wt.%, still more preferably 99.5 wt.% to 99.95 wt.% and most preferably 99.75 wt.% to 99.95 wt.% of the polyethylene composition.
Preferably, the base resin does not include 1-hexene.
Polyethylene composition
The polyethylene composition may further comprise additives and/or fillers. It is noted here that the additives may be present in the polymer (a) of ethylene and/or mixed with the base resin in the compounding step for producing the polyethylene composition. Examples of such additives are, inter alia, antioxidants, process stabilizers, ultraviolet light stabilizers, colorants, fillers, antistatic additives, antiblocking agents, nucleating agents, acid scavengers, slip agents and Polymer Processing Agents (PPA). Preferably, the total amount of these additives is 1.0 wt% or less of the polyethylene composition, more preferably 0.5 wt% or less, most preferably 0.25 wt% or less.
It is understood herein that any additive and/or filler may optionally be added to a so-called masterbatch comprising the corresponding additive or additives and carrier polymer. In this case, the carrier polymer is not calculated into the base resin of the polyethylene composition, but into the corresponding amount of one or more additives, based on the total amount of the polyethylene composition.
The polyethylene composition is characterized by the following properties:
MFR 2
the polyethylene composition preferably has a melt flow rate MFR measured according to ISO 1133 of from 0.7g/10min to 4.0g/10min, more preferably from 0.9g/10min to 3.0g/10min, still more preferably from 1.0g/10min to 2.5g/10min, even more preferably from 1.1g/10min to 2.0g/10min and most preferably from 1.2g/10min to 1.8g/10min 2 (190℃，2.16kg)。
MFR 21
The polyethylene composition preferably has a melt flow rate MFR according to ISO1133 of 15g/10min to less than 50g/10min, preferably 20g/10min to 45g/10min, still more preferably 23g/10min to 40g/10min and most preferably 25g/10min to 35g/10min 21 (190℃，21.6kg)。
FRR 21/2
The polyethylene composition preferably has a flow rate ratio FRR of from 10 to 30, more preferably from 12 to 27 and most preferably from 15 to 25 21/2 I.e. MFR 21 And MFR of 2 Is a ratio of (c).
Molecular weight distribution Mw/Mn
The polyethylene composition preferably has a polydispersity index PDI, i.e. the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn, in the range of 3.0 to 8.0, more preferably in the range of 3.5 to 7.5 and most preferably in the range of 4.0 to 6.0.
Density of
The polyethylene composition had a weight of 913.0kg/m 3 To 920.0kg/m 3 And preferably 914.0kg/m 3 To 919.0kg/m 3 Is determined according to ISO 1183-1:2004.
The density of the base resin is mainly affected by the amount and type of comonomer. In addition to this, the nature of the polymer, which originates mainly from the catalyst used, also plays a role in the melt flow rate.
In one embodiment, the present invention relates to a polyethylene composition comprising a base resin, wherein the base resin comprises
(A) A first ethylene-1-butene copolymer fraction (a) having a 1-butene content of 0.5 to 7.5% by weight based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (a) and a melt flow rate MFR measured according to ISO1133 at a temperature of 190 ℃ and a load of 2.16kg in the range of 1.0 to less than 50.0g/10min 2 The method comprises the steps of carrying out a first treatment on the surface of the And
(B) A second ethylene-1-butene copolymer fraction (B) having a 1-butene content of from 10.0 to 25.0% by weight and a melt flow rate MFR measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg of from 0.05g/10min to less than 1.0g/10min, based on the total weight of monomer units in the second ethylene-1-butene copolymer fraction (B) 2 ；
Wherein the base resin is polymerized in the presence of a single site catalyst system and the base resin has a weight of 913.0 to 920.0kg/m 3 And a 1-butene content of 8.0 to 13.0 wt% based on the total weight of monomer units in the base resin.
Article of manufacture
In still another aspect, the present invention relates to an article comprising a polyethylene composition as described above or below, obtainable by a process as described above or below, and the use of such a polyethylene composition for the production of an article.
The article is preferably a film or a blown or rotomoulded article.
It is particularly preferred that the article is a film, such as a blown film or a cast film or a multilayer film. In the multilayer film, the polyethylene composition is preferably included in one or more layers of the multilayer film.
The film comprising the polyethylene composition according to the invention is characterized by preferably having the following properties:
tensile modulus in machine direction (TM-MD)
Films comprising the polyethylene composition according to the invention preferably have a tensile modulus in machine direction (TM-TD) of at least 150MPa, more preferably at least 175MPa, measured according to ASTM D882 on 40 μm blown films at a test speed of 5mm/min and a strain of 1%. The upper limit of the longitudinal tensile modulus is generally not higher than 500MPa, preferably not higher than 300MPa.
Transverse tensile modulus (TM-TD)
Films comprising the polyethylene composition according to the invention preferably have a transverse tensile modulus (TM-TD) of at least 175MPa, more preferably at least 200MPa and most preferably at least 225MPa, measured according to ASTM D882 on a 40 μm blown film at a test speed of 5mm/min and a strain of 1%. The upper limit of the tensile modulus in the transverse direction is generally not higher than 500MPa, preferably not higher than 350MPa.
Tensile stress at Break in machine direction (TSB-MD)
The film comprising the polyethylene composition according to the invention preferably has a tensile stress at machine direction break (TSB-MD) of at least 30MPa, more preferably at least 35MPa and most preferably at least 40MPa, measured at a test speed of 500mm/min according to ISO 527-3:1996 on a 40 μm blown film. The upper limit of the tensile stress at longitudinal break is generally not higher than 100MPa, preferably not higher than 75MPa.
Transverse rupture tensile stress (TSB-TD)
The film comprising the polyethylene composition according to the invention preferably has a transverse direction tensile stress (TSB-TD) of at least 25MPa, more preferably at least 30MPa and most preferably at least 32MPa, measured on a 40 μm blown film according to ISO 527-3:1996 at a test speed of 500 mm/min. The upper limit of the tensile stress at transverse rupture is generally not higher than 100MPa, preferably not higher than 75MPa.
Tensile stress at yield in machine direction (TSY-MD)
The film comprising the polyethylene composition according to the invention preferably has a tensile stress in machine direction (TSY-MD) of at least 10MPa, more preferably at least 12MPa and most preferably at least 13MPa, measured at a test speed of 500mm/min according to ISO 527-3:1996 on 40 μm blown film. The upper limit of the tensile stress at longitudinal yield is generally not higher than 40MPa, preferably not higher than 30MPa.
Transverse yield tensile stress (TSY-TD)
The film comprising the polyethylene composition according to the invention preferably has a transverse direction tensile stress (TSY-TD) measured on a 40 μm blown film according to ISO 527-3:1996 at a test speed of 500mm/min of at least 8.0MPa, more preferably at least 9.0MPa and most preferably at least 10.0 MPa. The upper limit of the tensile stress at transverse yield is generally not higher than 40MPa, preferably not higher than 30MPa.
Elongation at break in machine direction (EB-MD)
The film comprising the polyethylene composition according to the invention preferably has an elongation at break in machine direction (EB-MD) measured according to ISO 527-3:1996 on 40 μm blown film at a test speed of 500mm/min of at least 500%, more preferably at least 550% and most preferably at least 575%. The upper limit of the elongation at break in the machine direction is generally not higher than 850%, preferably not higher than 800%.
Elongation at break in transverse direction (EB-TD)
The film comprising the polyethylene composition according to the invention preferably has an elongation at break in the transverse direction (EB-TD) of at least 650%, more preferably at least 675% and most preferably at least 700% measured on a 40 μm blown film according to ISO 527-3:1996 at a test speed of 500 mm/min. The upper limit of the elongation at break in the transverse direction is generally not higher than 1000%, preferably not higher than 900%.
Tear Strength in Elmendorf (TS-MD)
The film comprising the polyethylene composition according to the invention preferably has a tear strength in machine direction (TS-MD) of at least 0.6N, more preferably at least 0.7N and most preferably at least 0.8N measured on a 40 μm blown film according to ISO 6383-2:1983. The upper limit of the tear strength in the machine direction Elmendorf is generally not higher than 5.0N, preferably not higher than 4.0N.
Transverse Elmendorf tear Strength (TS-TD)
The film comprising the polyethylene composition according to the invention preferably has a transverse Elmendorf tear strength (TS-TD) as measured on a 40 μm blown film according to ISO 6383-2:1983 of at least 5.0N, more preferably at least 5.5N and most preferably at least 6.0N. The upper limit of the transverse Elmendorf tear strength is generally not higher than 20.0N, preferably not higher than 15.0N.
Tear Strength in Elmendorf (TS-MD)
The film comprising the polyethylene composition according to the invention preferably has a tear strength in machine direction (TS-MD) of at least 50g, more preferably at least 60g and most preferably at least 75g measured according to ISO 6383-2:1983 on 40 μm blown film. The upper limit of the tear strength in the machine direction Elmendorf is generally not higher than 500g, preferably not higher than 400g.
Transverse Elmendorf tear Strength (TS-TD)
The film comprising the polyethylene composition according to the invention preferably has a transverse Elmendorf tear strength (TS-TD) measured according to ISO 6383-2:1983 on a 40 μm blown film of at least 600g, more preferably at least 625g and most preferably at least 650 g. The upper limit of the tear strength in the transverse direction Elmendorf is generally not higher than 1000g, preferably not higher than 900g.
Puncture resistance-maximum force (PRF-max)
Films comprising the polyethylene composition according to the invention preferably have a puncture resistance-maximum force (PRF-max) of at least 20N, more preferably at least 22N and most preferably at least 25N, measured according to ASTM D5758 on 40 μm blown film at a test speed of 250 mm/min. The upper limit of the puncture resistance-maximum force (PRF-max) is generally not higher than 60N, preferably not higher than 55N.
Puncture resistance-breaking force (PRF-break)
Films comprising the polyethylene composition according to the invention preferably have a puncture resistance-break force (PRF-break) of at least 20N, more preferably at least 22N and most preferably at least 25N when measured according to ASTM D5758 on 40 μm blown film at a test speed of 250 mm/min. The upper limit of the puncture resistance-breaking force (PRF-break) is generally not higher than 60N, preferably not higher than 55N.
Puncture resistance-energy to break (PRE)
Films comprising the polyethylene composition according to the invention preferably have a puncture resistance-break energy (PRE) measured according to ASTM D5758 on 40 μm blown film at a test speed of 250mm/min of at least 0.50J, more preferably at least 0.55J and most preferably at least 0.60J. The upper limit of the puncture resistance-breaking energy (PRE) is generally not higher than 5.0J, preferably not higher than 4.5J.
Puncture resistance-breaking travel (PRT)
Films comprising the polyethylene composition according to the invention preferably have a puncture resistance-break travel (PRT) of not more than 100mm, more preferably not more than 90mm and most preferably not more than 85mm, measured at a test speed of 250mm/min according to ASTM D5758 on 40 μm blown film. The lower limit of the puncture resistance-to-break travel (PRT) is typically at least 30mm, preferably at least 40mm.
Dart Impact (DDI)
The film comprising the polyethylene composition according to the invention preferably has a dart impact (DDI) as measured on a 40 μm blown film of at least 100g, more preferably at least 125g and most preferably at least 150 g. The upper limit of dart impact is generally not more than 500g, preferably not more than 450g.
Seal Initiation Temperature (SIT)
The film comprising the polyethylene composition according to the invention preferably has a Seal Initiation Temperature (SIT) measured on a 40 μm blown film of not more than 100 ℃, more preferably not more than 98 ℃ and most preferably not more than 97 ℃. The lower limit of the Seal Initiation Temperature (SIT) is typically at least 90 ℃, more preferably at least 92 ℃.
Thermal bonding temperature
The film comprising the polyethylene composition according to the invention preferably has a hot tack temperature as measured on a 40 μm blown film of at least 88.0 ℃, more preferably at least 90 ℃ and most preferably at least 92 ℃. The upper limit of the heat-bonding temperature is usually not more than 97 ℃, more preferably not more than 95 ℃.
Haze degree
Films comprising the polyethylene composition according to the invention preferably have a haze of not more than 14.0%, more preferably not more than 13.0% and most preferably not more than 12.0% when measured according to ASTM D1003 on 40 μm blown film. The lower limit of haze is typically at least 2.0%, more preferably at least 3.0%.
Gloss level
The film comprising the polyethylene composition according to the invention preferably has a gloss as measured according to ISO 2813 on the inner surface of a 40 μm blown film of at least 92.0%, more preferably at least 95.0%, most preferably at least 98.0%. The upper limit of the gloss is usually not more than 115%, more preferably not more than 110%.
Gel content
Films comprising the polyethylene composition according to the invention preferably have a diameter of greater than 999 μm measured on a 70 μm cast film of no more than 10 gel/square meter, more preferably 6 gel/square meter and most preferably no gel/square meter.
The film comprising the polyethylene composition according to the invention preferably has a diameter of 600 to 999 μm measured on a 70 μm cast film of not more than 100 gel/square meter, more preferably not more than 60 gel/square meter and most preferably not more than 1.0 gel/square meter. The lower limit of the gel content of 600 to 999 μm in diameter is usually not less than 0.01 gel/square meter, more preferably not less than 0.1 gel/square meter.
The film comprising the polyethylene composition according to the invention preferably has a diameter of 300 to 599 μm as measured on a 70 μm cast film of not more than 250 gel per square meter, more preferably not more than 200 gel per square meter and most preferably not more than 170 gel per square meter. The lower limit of the gel content of 300 to 599 μm in diameter is usually not less than 5 gel/square meter, more preferably not less than 7 gel/square meter.
The film comprising the polyethylene composition according to the invention preferably has a diameter of 100 to 299 μm as measured on a 70 μm cast film of no more than 500 gel/square meter, more preferably no more than 400 gel/square meter and most preferably no more than 100 gel/square meter. The lower limit of the gel content of 100 to 299 μm is usually not less than 10 gel/square meter, more preferably not less than 20 gel/square meter.
Method
The polyethylene composition is produced in a process wherein the first and second ethylene-1-butene copolymers (a) and (B) are polymerized in the presence of a single site catalyst system in any order in a multistage process in at least two consecutive reactor stages.
Single site catalyst system
The first and second ethylene-1-butene copolymers (A) and (B) are preferably produced using a single site catalyst system comprising a metallocene catalyst and a non-metallocene catalyst, all terms having well known meanings in the art. The term "single site catalyst system" refers herein to a catalytically active metallocene compound or complex in combination with a cocatalyst. The metallocene compound or complex is also referred to herein as an organometallic compound.
The organometallic compounds include transition metals (M) of groups 3 to 10 or actinides or lanthanides of the periodic table (IUPAC 2007).
According to the present invention, the term "organometallic compound" includes any metallocene or non-metallocene compound of a transition metal bearing at least one organic (coordinating) ligand and exhibiting catalytic activity alone or together with a cocatalyst. Transition metal compounds are well known in the art, and the present invention encompasses compounds of metals of groups 3 to 10 (e.g., groups 3 to 7 or groups 3 to 6, such as groups 4 to 6 of the periodic table of elements (IUPAC 2007)) and lanthanides or actinides.
In one embodiment, the organometallic compound has the following formula (I):
(L) m R n MX q (I)
wherein the method comprises the steps of
"M" is a transition metal (M) of groups 3 to 10 of the periodic Table of the elements (IUPAC 2007),
each "X" is independently a monoanionic ligand, such as a sigma-ligand,
each "L" is independently an organic ligand coordinated to the transition metal "M",
"R" is a bridging group linking the organic ligands (L),
"m" is 1, 2 or 3, preferably 2,
"n" is 0, 1 or 2, preferably 1,
"q" is 1, 2 or 3, preferably 2, and
m+q is equal to the valence of the transition metal (M).
"M" is preferably selected from the group consisting of zirconium (Zr), hafnium (Hf) or titanium (Ti), more preferably from the group consisting of zirconium (Zr) and hafnium (Hf). "X" is preferably halogen, most preferably Cl.
Most preferably, the organometallic compound is a metallocene complex comprising a transition metal compound, as defined above, containing a cyclopentadienyl, indenyl or fluorenyl ligand as substituent "L". In addition, the ligand "L" may have a substituent such as an alkyl group, an aryl group, an aralkyl group, an alkylaryl group, a silane group, a siloxy group, an alkoxy group, or other hetero atom group, or the like. Suitable metallocene catalysts are known in the art and are disclosed in WO-A-95/12622, WO-A-96/32423, WO-A-97/28170, WO-A-98/32776, WO-A-99/61489, WO-A-03/010208, WO-A-03/051934, WO-A-03/051514, WO-A-2004/085499, EP-A-1752462 and EP-A-1739103.
The most preferred single site catalyst system is a metallocene catalyst system, which refers to a catalytically active metallocene complex as defined above together with a cocatalyst (also referred to as activator). Suitable activators are metal alkyls and especially aluminum alkyls as known in the art. Particularly suitable activators for use with metallocene catalysts are alkylaluminum oxides such as Methylaluminoxane (MAO), tetraisobutylaluminoxane (TIBAO) or Hexaisobutylaluminoxane (HIBAO).
More preferably, the first and second ethylene-1-butene copolymer fractions (a) and (B) are produced in the presence of the same single site catalyst system.
Details of the method are as follows:
the process for producing the polyethylene composition according to the invention comprises the steps of:
a) Polymerizing ethylene and 1-butene monomer in the presence of a single site catalyst system in a first polymerization reactor to form a first polymerization mixture comprising a first ethylene-1-butene copolymer fraction (a) having a 1-butene content of from 0.5 to 7.5% by weight based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (a) and a melt flow rate MFR measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg in the range of from 1.0 to less than 50.0g/10min, and said single site catalyst 2 ；
b) Transferring the first polymerization mixture from the first polymerization reactor to the second polymerization reactor;
c) Polymerizing ethylene and 1-butene monomer in the presence of a single site catalyst in the second polymerization reactor to form a second polymerization mixture comprising the first ethylene-1-butene copolymer fraction (a) and a second ethylene-1-butene copolymer fraction (B);
d) Recovering the second polymerization mixture from the second reactor;
e) Forming a powder having a weight of 913.0 to 920.0kg/m 3 A base resin having a 1-butene content of 8.0 to 13.0% by weight based on the total weight of monomer units in the base resin, and
f) A polyethylene composition was prepared.
The first ethylene-1-butene copolymer fraction produced in process step a) preferably represents the first ethylene-1-butene copolymer fraction (a) as defined hereinabove or hereinafter.
The second ethylene-1-butene copolymer fraction produced in process step c) preferably represents the second ethylene-1-butene copolymer fraction (B) as defined hereinabove or hereinafter.
The base resin formed in process step e) preferably represents a base resin as defined above or below.
The temperature in the first reactor, preferably the first slurry phase reactor, more preferably the first loop reactor is typically 50 to 115 ℃, preferably 60 to 110 ℃ and especially 70 to 100 ℃. The pressure is generally from 1 to 150 bar, preferably from 1 to 100 bar.
Slurry phase polymerization may be carried out in any known reactor for slurry phase polymerization. Such reactors include continuous stirred tank reactors and loop reactors. It is particularly preferred to carry out the polymerization in a loop reactor. In such reactors, the slurry is circulated at high speed along a closed pipe by using a circulation pump. Loop reactors are well known in the art and examples are given in e.g. US-se:Sup>A-4,582,816, US-se:Sup>A-3,405,109, US-se:Sup>A-3,324,093, EP-se:Sup>A-479 186 and US-se:Sup>A-5,391,654.
It is sometimes advantageous to carry out the slurry phase polymerization above the critical temperature and pressure of the fluid mixture. Such an operation is described in US-se:Sup>A-5,391,654. In such an operation, the temperature is generally at least 85 ℃, preferably at least 90 ℃. Furthermore, the temperature is generally not higher than 110 ℃, preferably not higher than 105 ℃. The pressure under these conditions is generally at least 40 bar, preferably at least 50 bar. Furthermore, the pressure is generally not higher than 150 bar, preferably not higher than 100 bar. In a preferred embodiment, the slurry phase polymerization step is carried out under supercritical conditions whereby the reaction temperature and reaction pressure are above the equivalent critical point of the mixture formed from the hydrocarbon medium, monomer, hydrogen and optional comonomer and the polymerization temperature is below the melting temperature of the polymer formed.
The slurry may be withdrawn from the slurry phase reactor continuously or intermittently. The preferred way of intermittent withdrawal is to concentrate the slurry using settling legs, after which a batch of concentrated slurry is withdrawn from the reactor. The use of settling legs is disclosed in US-A-3,374,211, US-A-3,242,150 and EP-A-1 310 295. Continuous extraction is disclosed in EP-A-891 990, EP-A-1 415 999, EP-A-1 591 460 and WO-A-2007/025640. The continuous withdrawal is advantageously combined with a suitable concentration process as disclosed in EP-A-1 415 999 and EP-A-1 591 460.
The settling legs are used to concentrate the slurry withdrawn from the reactor. Thus, the withdrawal flow contains more polymer per volume than the slurry average in the reactor. This has the advantage that less liquid needs to be circulated back to the reactor and therefore the cost of the apparatus is lower. In commercial scale plants, the fluid withdrawn with the polymer is vaporized in a flash tank and from there compressed with a compressor and recycled to the slurry phase reactor.
However, the settling legs intermittently withdraw polymer. This results in pressure and other variables in the reactor fluctuating with the withdrawal cycle. Furthermore, the extraction capacity is limited and depends on the size and number of settling legs. To overcome these drawbacks, continuous extraction is generally preferred.
On the other hand, the problem with continuous withdrawal is that it usually withdraws the polymer at the same concentration as that present in the reactor. In order to reduce the amount of hydrocarbons to be compressed, the continuous outlet is advantageously combined with a suitable concentrating device, such as a hydrocyclone or a screen, as disclosed in EP-a-1 415 999 and EP-a-1 591 460. The polymer-rich stream is then directed to a flash vessel and the polymer-lean stream is returned directly to the reactor.
To adjust the melt flow rate of the ethylene-1-butene fraction polymerized in the slurry phase reactor, hydrogen is preferably introduced into the reactor.
The hydrogen feed in the first reaction stage is preferably adjusted in dependence on the ethylene feed to achieve a hydrogen to ethylene ratio in the first slurry phase reactor of from 0.02 to 1.0mol/kmol, more preferably from 0.03 to 0.5 mol/kmol.
In addition to ethylene monomer, 1-butene comonomer is added to the slurry phase reactor to produce a first ethylene-1-butene copolymer fraction.
The 1-butene feed in the first reaction stage is preferably adjusted in accordance with the ethylene feed to achieve a 1-butene to ethylene ratio in the first slurry phase reactor of from 50 to 200mol/kmol, more preferably from 80 to 150 mol/kmol.
It is preferred that no further comonomer other than 1-butene is introduced into the primary slurry phase reactor.
The residence time and polymerization temperature in the first slurry phase reactor are adjusted such that the amount of polymerized ethylene-1-butene copolymer fraction is typically from 30 to 47 wt%, more preferably from 32 to 46 wt% and most preferably from 35 to 45 wt% of the total base resin.
The polymer slurry may be subjected to a flash step to substantially remove hydrocarbons from the polymer slurry prior to being introduced into the second polymerization reactor. After the application of the flash step, the first polymerization mixture produced in the first slurry reactor is preferably transferred to a second reactor, preferably a gas phase reactor, more preferably a fluidized bed gas phase reactor.
In a fluidized bed gas phase reactor, olefins are polymerized in an upwardly moving gas stream in the presence of a polymerization catalyst. The reactor typically contains a fluidized bed comprising growing polymer particles containing active catalyst above a fluidization grid.
The polymer bed is fluidized with the aid of a fluidizing gas comprising olefin monomer, eventually one or more comonomers, eventually a chain growth control agent or chain transfer agent, such as hydrogen and eventually an inert gas. Thus, the inert gas may be the same as or different from the inert gas used in the slurry phase reactor. The fluidizing gas is introduced into the inlet chamber at the bottom of the reactor. In order to ensure se:Sup>A uniform distribution of the air flow over the cross-sectional surface arese:Sup>A of the inlet chamber, the inlet duct may be provided with flow dividing elements known in the art, for example US-se:Sup>A-4,933,149 and EP-se:Sup>A-684 871.
The gas flow passes from the inlet chamber up through the fluidization grid into the fluidized bed. The purpose of the fluidization grid is to evenly distribute the gas flow through the cross-sectional area of the bed. Sometimes, the fluidization grid may be arranged to let the gas flow to sweep along the reactor wall, as disclosed in WO-A-2005/087261. Other types of fluidization grids are disclosed in US-A-4,578,879, EP 600 414 and EP-A-721 798. In Geldart and Bayens: the Design of Distributors for Gas-fluidized Beds, powder Technology, volume 42, summarized in 1985.
The fluidizing gas passes through the fluidized bed. The superficial velocity of the fluidization gas must be higher than the minimum fluidization velocity of the particles contained in the fluidized bed, otherwise fluidization does not occur. On the other hand, the velocity of the gas should be lower than the initial velocity of the pneumatic transport, otherwise the whole bed will be entrained with the fluidizing gas. When the particle characteristics are known, the minimum fluidization velocity and the initial velocity of the pneumatic transport can be calculated by using common engineering practices. At Geldart: gas Fluidisation Technology, J.Wiley & Sons, 1996.
When the fluidizing gas is contacted with a bed containing an active catalyst, the active components of the gas (such as monomers and chain transfer agents) react in the presence of the catalyst to produce a polymer product. While the gas is heated by the heat of reaction.
Unreacted fluidizing gas is then removed from the top of the reactor, compressed and recycled to the inlet chamber of the reactor. Fresh reactants are introduced into the fluidization gas stream prior to entering the reactor to compensate for losses caused by reaction and product withdrawal. It is well known to analyze the composition of the fluidizing gas and introduce gas components to keep the composition constant. The actual composition is determined by the desired properties of the product and the catalyst used in the polymerization.
Thereafter, the gas is cooled in a heat exchanger to remove the heat of reaction. The gas is cooled to a temperature below the bed to prevent the bed from being heated by the reaction. The gas may be cooled to a temperature at which part of the gas condenses. As the droplets enter the reaction zone they are vaporized. The heat of vaporization then helps to remove the heat of reaction. This operation is called the concentrate mode and variants thereof are disclosed in WO-A-2007/025640, US-A-4,543,399, EP-A-699 213 and WO-A-94/25495. Condensing agents may also be added to the recycle gas stream, as disclosed in EP-a-696 293. Condensing agents are non-polymerizable components such as propane, n-pentane, isopentane, n-butane or isobutane that condense at least partially in the cooler.
The polymer product may be withdrawn from the gas phase reactor continuously or intermittently. Combinations of these methods may also be used. Continuous withdrawal is disclosed, inter aliA, in WO-A-00/29452. Intermittent extraction is disclosed, inter alise:Sup>A, in U.S. Pat. No. 4,621,952, EP-A-188 125, EP-A-250 169 and EP-A-579 426.
The top of the at least one gas phase reactor may comprise a so-called separation zone. In such a zone, the diameter of the reactor is increased to reduce the gas velocity and allow particles entrained from the bed to settle back into the bed with the fluidizing gas.
Bed levels may be observed by different techniques known in the art. For example, the pressure difference between the bottom of the reactor and a particular height of the bed may be recorded over the entire length of the reactor, and the bed level may be calculated based on the pressure difference value. Such calculations produce a time-averaged level. Ultrasonic or radiological sensors may also be used. Using these methods, instantaneous levels can be obtained, and these levels can then of course be averaged over a period of time to obtain a time-averaged bed level.
If desired, one or more antistatics can also be introduced into the at least one gas-phase reactor. Suitable antistatics and methods of using them are disclosed in U.S. Pat. No. 5,026,795, U.S. Pat. No. 4,803,251, U.S. Pat. No. 4,532,311, U.S. Pat. No. 4,855,370 and EP-A-560 035. They are generally polar compounds and include, inter alia, water, ketones, alditols.
The reactor may include a mechanical agitator to further promote mixing within the fluidized bed. Examples of suitable stirrer designs are given in EP-A-707 513.
The temperature of the gas phase polymerization in the gas phase reactor is generally at least 70 ℃, preferably at least 80 ℃. The temperature is generally not more than 105 ℃, preferably not more than 95 ℃. The pressure is generally at least 10 bar, preferably at least 15 bar but generally not more than 30 bar, preferably not more than 25 bar.
To adjust the melt flow rate of the ethylene-1-butene copolymer fraction polymerized in the gas phase reactor, hydrogen is preferably introduced into the reactor.
The hydrogen feed is preferably adjusted to achieve a hydrogen to ethylene ratio of from 0.2 to 1.5mol/kmol, more preferably from 0.2 to 1.0mol/kmol and most preferably from 0.3 to 0.8mol/kmol in the gas phase reactor, depending on the ethylene feed.
A second ethylene-1-butene copolymer fraction is produced in the gas phase reactor.
The 1-butene feed is preferably adjusted according to the ethylene feed to achieve a comonomer to ethylene ratio of at least 100 to 300mol/kmol, more preferably 125 to 225mol/kmol, most preferably 150 to 200 mol/kmol.
The reaction mixture in the gas phase reactor may contain a comonomer other than 1-butene, such as, for example, an alpha-olefin comonomer, such as 1-hexene. The comonomer other than 1-butene may be traces of comonomers, which are residues of the previous polymerization carried out in the gas phase reactor. Traces of other residual comonomer may also be removed by techniques known in the art, such as purging with 1-butene. Preferably, no comonomer other than 1-butene is fed to the gas phase reactor during polymerization of the polyethylene composition of the invention. It is further preferred that during the polymerization of the polyethylene composition of the invention, no comonomer other than 1-butene is present in the gas phase reactor.
The residence time in the gas phase reactor and the polymerization temperature are adjusted such that the amount of the second ethylene-1-butene copolymer fraction polymerized is typically 43 to 65 wt. -%, more preferably 44 to 62 wt. -% and most preferably 45 to 60 wt. -% of the total base resin.
Furthermore, the final base resin coming out of the gas phase reactor, preferably consisting of the first and second ethylene-1-butene copolymer fractions, has a weight of 913.0kg/m 3 To 920.0kg/m 3 And preferably 914.0kg/m 3 To 918.0kg/m 3 Is a density of (3).
The polymerization of the first and second ethylene-1-butene copolymer fractions in the first and second polymerization stages may be preceded by a prepolymerization step. The purpose of the prepolymerization is to polymerize small amounts of polymer onto the catalyst at low temperatures and/or low monomer concentrations. By pre-polymerization, the performance of the catalyst in the slurry can be improved and/or the final polymer properties can be altered. The prepolymerization step can be carried out in slurry or gas phase. The prepolymerization is preferably carried out in a slurry, preferably in a loop reactor. The prepolymerization is then preferably carried out in an inert diluent, preferably a low boiling hydrocarbon having 1 to 4 carbon atoms or a mixture of these hydrocarbons.
The temperature in the prepolymerization step is usually 0 to 90 ℃, preferably 20 to 80 ℃ and more preferably 40 to 70 ℃.
The pressure is not critical and is generally from 1 to 150 bar, preferably from 10 to 100 bar.
When a single site catalyst system is present, it may be fed to any polymerization stage, but preferably to the first polymerization stage or the pre-polymerization stage. The catalyst component is preferably introduced in its entirety into the prepolymerization step. Preferably, the reaction product of the prepolymerization step is then introduced into the first polymerization reactor. The prepolymer component is calculated as the amount of the component produced in the first actual polymerization step after the prepolymerization step, preferably as the amount of the low molecular weight ethylene polymer component.
Compounding
The polyethylene composition of the invention is preferably produced in a multistage process, which further comprises a compounding step, wherein the base resin, typically obtained as a base resin powder from the reactor, is extruded in an extruder and then pelletized into polymer pellets in a manner known in the art to form the polyolefin composition of the invention.
Optionally, additives or other polymer components may be added to the composition during the compounding step in amounts as described above. Preferably, the composition of the invention obtained from the reactor is compounded in an extruder together with additives and optional polymers different from the first and second ethylene-1-butene copolymer fractions (a) and (B) as defined above in a manner known in the art.
For example, the extruder may be any conventionally used extruder. Examples of extruders for the compounding step of the present invention may be those provided by Japan Steel works, kobe Steel or Farrel-Pomini, such as JSW 460P or JSW CIM90P.
Film production
The polymer films are generally produced by blown film extrusion or by cast film extrusion.
In the case of multilayer films, several films may be coextruded or laminated during blown film extrusion or cast film extrusion.
These methods are well known in the art and are readily adaptable for use in producing films comprising the polyethylene composition according to the invention.
Use of the same
The invention further relates to the use of a polyethylene composition as defined hereinabove or hereinafter for the production of an article such as a film as described hereinabove or hereinafter.
Examples
1. Measurement method
a) Melt flow Rate
Melt Flow Rate (MFR) is determined according to ISO 1133 and is expressed in g/10 min. MFR indicates the flowability of the polymer and thus the processability of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR of the polyethylene is determined at 190 ℃. The MFR can be determined under different loads, such as 2.16kg (MFR 2 )、5kg(MFR 5 ) Or 21.6kg (MFR) 21 )。
2 MFR (190) of the second ethylene-1-butene copolymer fraction (B)℃2.16 kg)
MFR of the second ethylene-1-butene copolymer fraction (B) 2 (calculation of 190 ℃,2.16 kg):
wherein the method comprises the steps of
w (A) is the weight fraction [ in weight%) of the first ethylene-1-butene copolymer fraction (A) in the blend of polymer fractions A and B,
w (B) is the weight fraction [ in weight%) of the second ethylene-1-butene copolymer fraction (B) in the blend of polymer fractions A and B,
MFR (A) is the melt flow Rate MFR of the first ethylene-1-butene copolymer fraction (A) 2 (190 ℃ C., 2.16 kg) [ in g/10min ]]，
MFR (A+B) is the melt flow Rate MFR of the blend of Polymer fractions A and B 2 (190 ℃ C., 2.16 kg) [ in g/10min ]]，
MFR (B) is the calculated melt flow Rate MFR of the second ethylene-1-butene copolymer fraction (B) 2 (190 ℃ C., 2.16 kg) [ in g/10min ]]。
b) Density of
The density of the polymer is according to ASTM; d792, method B (by balancing the density at 23 ℃) was measured on compression molded samples prepared according to EN ISO 1872-2 (month 2 2007) in kg/m 3 。
Calculation of the Density of the second ethylene-1-butene copolymer fraction (B)
Calculation of the density of the second ethylene-1-butene copolymer fraction (B):
Wherein the method comprises the steps of
w (A) is the weight fraction [ in weight%) of the first ethylene-1-butene copolymer fraction (A) in the blend of polymer fractions A and B,
w (B) is the weight fraction [ in weight%) of the second ethylene-1-butene copolymer fraction (B) in the blend of polymer fractions A and B,
density (A) is the Density in kg/m of the first ethylene-1-butene copolymer fraction (A) 3 Meter with a meter body]，
Density (A+B) is the density in kg/m of the blend of polymer fractions A and B 3 Meter with a meter body]，
Density (B) is the calculated Density in kg/m of the second ethylene-1-butene copolymer fraction (B) 3 Meter with a meter body]。
c) Molecular weight, molecular weight distribution (Mn, mw, MWD) -GPC
PL 220 (Agilent) GPC was used, equipped with a Refractometer (RI), an in-line four-capillary bridge viscometer (PL-BV 400-HT), and a double light scattering detector with angles of 15℃and 90 ℃. 3x oxides and 1x oxides Guard from Agilent were used as stationary phase and 1,2, 4-trichlorobenzene (TCB, stabilized with 250mg/L of 2, 6-di-tert-butyl-4-methylphenol) was used as mobile phase at 160 ℃ and at a constant flow rate of 1 mL/min. 200. Mu.L of sample solution was injected for each analysis. All samples were prepared by dissolving 8.0 to 12.0mg of polymer in 10mL (160 ℃ C.) of stabilized TCB (same mobile phase) and continuing to gently shake at 160 ℃ for 2.5h (PP) or 3h (PE). Injection concentration of Polymer solution at 160 ℃ (c) 160 DEG C) is determined according to the following manner.
/>
Wherein: w (w) 25 (Polymer weight) and V 25 (TCB volume at 25 ℃).
The corresponding detector constants and the inter-detector delay volumes were determined with a narrow PS standard (mwd=1.01) with a molar mass of 132900g/mol and a viscosity of 0.4789 dl/g. The corresponding dn/dc of the PS standard used in TCB is 0.053cm 3 And/g. Calculations were performed using Cirrus Multi-Offline SEC software version 3.2 (Agilent).
The molar mass of each elution slice was calculated by using a 15 ° light scattering angle. Data collection, data processing and calculation were performed using Cirrus Multi SEC software version 3.2. Molecular weights were calculated using "sample calculation options in Cirrus software subfield slice MW data from" options in field "using LS 15 angle". The dn/dc for determining molecular weight is calculated from the detector constant of the RI detector, the concentration c of the sample, and the detector response area of the analyzed sample.
The molecular weight of each slice was calculated at low angles in the manner described in c.jackson and h.g. barth ("Molecular Weight Sensitive Detectors" in c.jackson and h.g. barth, handbook ofSize Exclusion Chromatography and related technology, c. -s.wu, 2 nd edition, marcel Dekker, new york, 2004, page 103). For the low and high molecular regions, respectively, where less signal is obtained for the LS or RI detector, a linear fit is used to relate the elution volume to the corresponding molecular weight. The area of the linear fit was adjusted according to the sample.
Average molecular weight (Mz, mw, and Mn), molecular Weight Distribution (MWD), and breadth thereof, are determined by Gel Permeation Chromatography (GPC), described by the polydispersity index pdi=mw/Mn (where Mn is the number average molecular weight, mw is the weight average molecular weight), according to ISO 16014-4:2003 and ASTM D6474-99, calculated using the following formulas:
for a constant elution volume interval DeltaV i Wherein A is i And M i Is the chromatographic peak slice area and polyolefin Molecular Weight (MW) as determined by GPC-LS.
d) Comonomer content:
quantification of microstructure by NMR spectroscopy
Quantitative Nuclear Magnetic Resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymer.
Use of the device 1 H and 13 c Bruker Avance III NMR spectrometer operating at 500.13 and 125.76MHz respectively records quantification in the molten state 13 C{ 1 H } NMR spectra. Nitrogen was used for all pneumatic devices at 150 ℃ 13 C optimized 7mm magic angle turning (MAS) probe recorded all spectra. About 200mg of material was charged into a zirconia MAS rotor having an outer diameter of 7mmAnd rotated at 4 kHz. This setup was chosen primarily for rapid identification and accurate quantification of the required high sensitivity { klimke06, parkinson07, castignoles 09}. With standard monopulse excitation, NOE { polar 04, klimke06} and RS-HEPT decoupling schemes { filelip 05, griffin07} are utilized with short cyclic delays. A total of 1024 (1 k) transient signals are acquired per spectrum.
Will be quantified 13 C{ 1 The H } NMR spectrum is processed, integrated and the quantitative nature of the correlation is determined from the integration. All chemical shifts are referenced internally to the bulk methylene signal (δ+) at 30.00 ppm.
Using the integration of the methylene (δ+) sites at 30.00ppm, the amount of ethylene was quantified taking into account the number of reporting sites per monomer:
E＝I δ+ /2
the presence of isolated comonomer units is corrected based on the number of isolated comonomer units present:
eTotal=E+ (3×B+2×H)/2
Wherein B and H are defined as their corresponding comonomers. If continuously and discontinuously incorporated comonomers are present, they are corrected in a similar manner.
A characteristic signal corresponding to the incorporation of 1-butene was observed and the comonomer fraction was calculated as the fraction of 1-butene in the polymer with respect to all monomers in the polymer:
fBTotal= (BTotal/(ETotal+BTotal+HTotal)
Using the integration of the B2 sites at 38.3ppm, the amount of isolated 1-butene incorporated in the EEBEE sequence was quantified taking into account the number of reporting sites per comonomer:
B＝I *B2
using the integration of the ααb2b2 site at 39.4ppm, the amount of continuous incorporation of 1-butene in the EEBBEE sequence was quantified taking into account the number of reporting sites per comonomer:
BB＝2*IααB2B2
Using the integration of ββb2b2 sites at 24.7ppm, the amount of discontinuously incorporated 1-butene in the eebee sequence was quantified taking into account the number of reporting sites per comonomer:
BEB＝2*IββB2B2
since the respective B2 and βb2b2 sites of isolated (EEBEE) and non-continuously incorporated (EEBEE) 1-butene overlap, the total amount of isolated 1-butene is corrected based on the amount of non-continuous 1-butene present:
B＝I *B2 -2*I ββB2B2
based on the sum of isolated, continuous and discontinuous incorporation of 1-butene, the total content of 1-butene was calculated:
balways=b+bb+beb
The total mole fraction of 1-butene in the polymer was then calculated as:
fb= (btal/(E total + btal + htal)
A characteristic signal corresponding to the incorporation of 1-hexene was observed and the comonomer fraction was calculated as the fraction of 1-hexene in the polymer with respect to all monomers in the polymer:
fH total= (htotal/(E total + B total + H total))
Using integration of the B4 sites at 39.9ppm, the amount of isolated 1-hexene incorporated in the EEHEE sequence was quantified taking into account the number of reporting sites per comonomer:
H＝I *B4
using the integration of the ααb4b4b4 site at 40.5ppm, the amount of continuously incorporated 1-hexene in the EEHHEE sequence was quantified taking into account the number of reporting sites per comonomer:
HH＝2*IααB4B4
Using the integration of the ββb4b4b4 sites at 24.7ppm, the amount of discontinuously incorporated 1-hexene in the eehee sequence was quantified taking into account the number of reporting sites per comonomer:
HEH＝2*IββB4B4
the total mole fraction of 1-hexene in the polymer was then calculated as:
fh= (hgal/(E total + B total + hgal))
The mole percent of comonomer incorporated was calculated from the mole fraction:
b [ mol% ] =100×fb
H [ mol% ] = 100 x fh
The weight percent of comonomer incorporated was calculated from the mole fraction:
b [ wt% ] =100 (fB 56.11)/((fB 56.11) + (fH 84.16) + (1- (fb+fh)). 28.05)
H [ wt% ] =100× (fh×84.16)/((fb×56.11) + (fh×84.16) + (1- (fb+fh))× 28.05)
Reference is made to:
klimke06
Klimke,K.,Parkinson,M.,Piel,C.,Kaminsky,W.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2006；207:382.
parkinson07
Parkinson,M.,Klimke,K.,Spiess,H.W.,Wilhelm,M.,Macromol.Chem.Phys.2007；208:2128.
pollard04
Pollard,M.,Klimke,K.,Graf,R.,Spiess,H.W.,Wilhelm,M.,Sperber,O.,Piel,C.,Kaminsky,W.,Macromolecules 2004；37:813.
filip05
Filip,X.,Tripon,C.,Filip,C.,J.Mag.Resn.2005,176,239.
griffin07
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calculation of the 1-butene comonomer content of the second ethylene-1-butene copolymer fraction (B)
Calculation of 1-butene content of the second ethylene-1-butene copolymer fraction (B):
wherein the method comprises the steps of
w (A) is the weight fraction [ in weight%) of the first ethylene-1-butene copolymer fraction (A) in the blend of polymer fractions A and B,
w (B) is the weight fraction [ in weight%) of the second ethylene-1-butene copolymer fraction (B) in the blend of polymer fractions A and B,
c (A) is the 1-butene comonomer content in wt.% of the first ethylene-1-butene copolymer fraction (A),
C (A+B) is the 1-butene comonomer content in wt% of the blend of polymer fractions A and B,
c (B) is the calculated 1-butene comonomer content in wt.% of the second ethylene-1-butene copolymer fraction (B).
e) Tensile Properties of the film
Film tensile properties were measured according to ISO 527-3 using 40 μm thick blown films at 23℃using sample type 2. Film samples were produced as described in the experimental section below.
The tensile modulus in the machine direction (TM-MD) and the tensile modulus in the transverse direction (TM-TD) were measured at a test speed of 5mm/min and a gauge length of 50mm according to ASTM D882 at a secant modulus of 1%.
Tensile strength at break (TSB-MD and TSB-TD), tensile strength at yield (TSY-MD and TSY-TD) and elongation at break (EB-MD) were measured according to ISO 527-3 sample type 2 at a gauge length of 50mm and a test speed of 500 mm/min.
f) Tear strength (measured as Elmendorf tear strength): machine Direction (MD) and Transverse Direction (TD)
Tear tests were performed on 40 μm blown films according to ASTM 1922. The production of film samples is described in the experimental section below.
Elmendorf tear strength is the newtonian force required to propagate a tear on a film sample. It is measured using a precisely calibrated pendulum device. Under the action of gravity, the pendulum swings through an arc, tearing the specimen from the pre-cut slit. One side of the sample is fixed by a pendulum bob, and the other side is fixed by a fixing part. The energy loss of the pendulum is indicated by a pointer. The scale indicates the force required to tear the specimen. The weight of the pendulum is selected based on the absorbed energy of the sample, preferably between 20 and 80% of the pendulum's capacity. There was no direct linear relationship between tear force and sample thickness. Therefore, only data obtained in the same thickness range should be compared.
g) Puncture resistance
Outstanding puncture resistance experiments were performed on 40 μm blown films according to ASTM D5748. The test method determines the penetration resistance of a film sample to a specific size 19mm diameter coated probe of pear-shaped TFE fluorocarbon at a standard low rate, single test speed (250 mm/min). The test method was performed under standard conditions, and imparted a biaxial stress load. Film samples were cut 150mm by 150mm to accommodate the clamps and conditioned at 23.+ -. 2 ℃ and 50.+ -. 5% relative humidity.
Puncture resistance force (N) is the maximum or highest force observed during testing, puncture resistance energy (J) is the energy used before the probe breaks the sample, both measured using a high precision 500N load cell and a crosshead position sensor.
h) Dart drop strength
Using ISO7765-1, method A (an alternative test technique) measures darts from film samples. A dart with a 38mm diameter hemispherical head falls from a height of 0.66m onto the film clamped to the hole. Groups of 20 samples were tested consecutively. One weight per group is used and the weight increases (or decreases) from group to group in uniform increments. The weight resulting in 50% specimen failure was calculated and reported.
i) Sealing performance:
The hot tack temperature and hot tack force were measured according to ASTM F1921-98 (2004), method B, using film samples having a thickness of 40 μm, which were produced as described in the "Experimental section" below. The following was used for the hot tack setup at hot tack temperature:
thermal bonding temperature(lowest temperature at which maximum hot tack is obtained) andthermal bonding(maximum hot tack) is measured according to the following settings:
q-instrument name: hot sticking-sealing tester
Model: j & B model 4000MB
Length of the sealing strip: 50[ mm ]
Width of sealing strip: 5[ mm ]
Sealing strip shape: flat panel
And (3) coating a sealing strip:
roughness of the sealing strip: 1[ mu m ]
Sealing temperature: variable [ DEGC ]
Sealing time: 1 s
Cooling time: 0.2 s
Sealing pressure: 0.15[ N/mm ] 2 ]
Clamp separation speed: 200[ mm/s ]
Sample width: 25[ mm ]
Sealing temperature:
the following settings were used. Film samples 40 μm thick were produced as described in the experimental section below.
Q-instrument name: hot tack seal tester 2
Model: j & B model 4000MB
Length of the sealing strip: 50[ mm ]
Width of sealing strip: 5[ mm ]
Sealing strip shape: flat panel
And (3) coating a sealing strip:
roughness of the sealing strip: 1[ mu m ]
Sealing temperature: variable [ DEGC ]
Sealing time: 1 s
Cooling time: 30 s
Sealing pressure: 0.4[ N/mm ] 2 ]
Clamp separation speed: 42[ mm/s ]
Sample width: 25[ mm ]
j) Haze degree
Haze measured according to ASTM D1003 on film samples having a thickness of 40 μm, these samples were produced as described in the experimental section below.
k) Gloss level
Gloss measured at angles of 20 °, 65 ° and 85 ° according to ISO 2813 on the inner surface of 40 μm thick film samples, which were produced as described in the experimental section below.
l) gel content determination:
gel number:
cast film samples of approximately 70 μm thickness were extruded and examined with a CCD (charge-coupled device) camera, an image processor and evaluation software (instrument: OCS-FSA100, supplier OCS GmbH (optical control system)). The thin film defects are measured and classified according to their size (longest dimension).
Cast film preparation and extrusion parameters:
1. yield 25.+ -.4 g/min
2. Extruder temperature profile: 230-230-230-220-210 (melting temperature 223 ℃ C.)
3. The film thickness was about 70. Mu.m
4. The temperature of the cooling roller is 55 to 65 DEG C
5. No Airkife is required
Extruder technical data:
1. screw type: zone 3, nitrified
2. Screw diameter: 25mm of
3. Screw length: 25D (25D)
4. Feeding area: 10D (10D)
5. Compression zone: 4D (4D)
6. And (3) a mold: 100mm of
According to the defect size (μm)/m 2 Classification is carried out:
100-299
300-599
600-999
>999
2. experimental part
a) Preparation of examples
Catalyst preparation
130g of the metallocene complex bis (1-methyl-3-n-butylcyclopentadienyl) zirconium (IV) dichloride (CAS No. 151840-68-5) and 9.67kg of a 30% commercial Methylaluminoxane (MAO) in toluene were mixed and 3.18kg of dry, purified toluene was added. The composite solution thus obtained was added to 17kg of silica support Sylopol 55SJ (supplied by GRACE) by a very slow uniform spray over 2 hours. The temperature was kept below 30 ℃. After the complex addition at 30℃the mixture was allowed to react for 3 hours.
Aggregation of inventive example IE 1:
prepolymerization:
volume of 50dm 3 The loop reactor was operated at a temperature of 60℃and a pressure of 65 bar. 2.5kg/h of ethylene, 30kg/h of propane diluent and 50g/h of 1-butene were introduced into the reactor. 16g/h of the catalyst described above were also introduced into the reactor. The polymer productivity was about 2kg/h.
Polymerization:
the slurry was intermittently withdrawn from the reactor and introduced into a volume of 500dm 3 And a loop reactor operating at a temperature of 85 ℃ and a pressure of 64 bar. 25kg/h of propane and ethylene and also 1-butene comonomer and hydrogen were further fed into the reactor so that the ethylene content in the reaction mixture was 4 mol%, the molar ratio of hydrogen to ethylene was 0.08mol/kmol and the ratio of 1-butene to ethylene was 110mol/kmol. The ethylene copolymer had a melt index MFR of 6.0g/10min 2 And 940kg/m 3 Density of BThe productivity of the olefin copolymer was 50kg/h.
Slurry was intermittently withdrawn from the loop reactor by using settling legs and led to a flash vessel operating at a temperature of 50 ℃ and a pressure of 3 bar. From there the polymer was led to a Gas Phase Reactor (GPR) operated at a pressure of 20 bar and a temperature of 75 ℃. Additional ethylene, 1-butene comonomer, nitrogen as inert gas and hydrogen were added so that the ethylene content in the reaction mixture was 37 mole%, the hydrogen to ethylene ratio was 0.35 mole/kmol, and the 1-butene to ethylene ratio was 175 mole/kmol. The polymer productivity in the gas phase reactor was 70kg/h, and thus the total polymer withdrawal rate from the gas phase reactor was 122kg/h. The polymer had a melt index MFR of 1.5g/10min 2 And 918kg/m 3 Is a density of (3). The production split (% loop/% GPR component) was 42/58. The amount of prepolymerization product is calculated as the amount of loop product.
The polymer was mixed with 1920ppm Irgafos 168, 480ppm Irganox 1010 (both commercially available from BASF SE) and 270ppm Dynamar FX5922 (commercially available from 3M company). It was then compounded and extruded into pellets by using a CIMP90 extruder under a nitrogen atmosphere such that the SEI was 230kWh/kg and the melt temperature was 250 ℃.
Aggregation of embodiment IE2 of the invention:
the polymer fraction of inventive example IE2 was produced according to inventive example 1, but using the polymerization conditions given in table 1. The polymer was mixed with 2400ppm Irgafos 168, 600ppm Irganox 1010 (both commercially available from BASF SE), 400ppm Dynamar FX5922 (commercially available from 3M company), 1000ppm Crodamide ER (commercially available from Croda), 1875ppm Silton JC-30 (commercially available from Mizusawa Ind. Chem.) and 625ppm Silton JC-50 (commercially available from Mizusawa Ind. Chem.). It was then compounded and extruded into pellets by using a CIMP90 extruder under a nitrogen atmosphere such that the SEI was 230kWh/kg and the melt temperature was 250 ℃.
Polymerization of reference example RE 3:
the polymer fraction of reference example RE3 was produced according to inventive example 1, but using the polymerization conditions given in table 1. In the gas phase reactor, 1-hexene was used as comonomer instead of 1-butene. The same additive package as the IE1 polymer of the present invention was used.
Preparation of the blend composition:
inventive blend IE1:
90% by weight of the final polymer composition according to example IE1 of the invention and 10% by weight of a commercial linear low density polyethylene produced in a high pressure process, under the trade name FT5230 (vendor Borealis, MFR 2 :0.75g/10min; density: 923kg/m 3 Tensile modulus MD of 230 MPa).
Inventive blend IE2:
90% by weight of the final polymer composition of inventive example IE2 and 10% by weight of FT5230.
Reference blend RE3:
90 wt% of the final polymer composition of reference example RE3 and 10 wt% FT5230.
Comparative blend CE4:
90% by weight of a final polymer composition (commercially available from Sabic) of LLDPE grade 118W for blown film extrusion, which is a unimodal metallocene-catalyzed ethylene-1-butene copolymer having an MFR of 1.0g/10min, and 10% by weight of FT5230 2 ，918kg/m 3 And a tensile modulus MD of 220 MPa.
The weight percentages are based on the total amount of the two polymer components.
Film sample preparation
A 5-layer coextrusion blown film line (Hosokawa Alpine) was used to prepare a test film consisting of a 40 μm thick blend composition as described above.
The apparatus had 5 extruders, the screw diameter of the 4 extruders of the apparatus was 65mm and the screw diameter of the 1 extruder was 90mm (the middle extruder was the largest). The width of the die is: 400mm, die gap 1.8mm, film thickness 40 μm.
Blow-up ratio (BUR): 2.5
-temperature profile, c: 30-190-190-190-190-190-195-195-195-extruder temperature profile was the same for all 5 extruders, throughput of 60kg/h per extruder
Die temperature 205 ℃, die temperature profile for all 5 extruders being the same
-FLH: 2 times of the diameter of the die
The two polymer components of the blend composition are dry blended prior to feeding to the extruder.
Table 1: polymerization conditions and Polymer Properties
Table 2: properties of blown films of blend compositions IE1, IE2, RE3 and CE4
| Unit (B) | IE1 | IE2 | RE3 | CE4 | |
| Tensile Modulus (MD) | MPa | 209 | 189 | 218 | 192 |
| Tensile modulus (TD) | MPa | 255 | 233 | 250 | 220 |
| TSY-MD | MPa | 15.7 | 15.2 | 15.7 | 14.4 |
| TSY-TD | MPa | 11.6 | 11.3 | 11.6 | 10.6 |
| TSB-MD | MPa | 48.6 | 44.7 | 45.7 | 38.8 |
| TSB-TD | MPa | 35.0 | 35.9 | 41.9 | 30.7 |
| EB-MD | ％ | 620 | 617 | 544 | 554 |
| EB-TS | ％ | 710 | 794 | 656 | 660 |
| Tear strength (MD) | N | 0.9 | 1.1 | 3.4 | 2.4 |
| Tear strength (TD) | N | 6.3 | 7.0 | 9.7 | 10.0 |
| Tear strength (MD) | g | 91 | 116 | 347 | 246 |
| Tear strength (TD) | g | 644 | 718 | 986 | 1019 |
| Maximum puncture force | N | 38.1 | 27.5 | 30.3 | 32.2 |
| Breaking puncture force | N | 31.7 | 27.0 | 30.2 | 32.2 |
| Penetration stroke at break | mm | 80.9 | 51.1 | 49.6 | 52.5 |
| Breaking puncture energy | J | 2.2 | 1.0 | 1.1 | 1.2 |
| DDI | g | 170 | 205 | 345 | 70 |
| SIT | ℃ | 96 | 96 | 91 | 106 |
| Thermal bonding | ℃ | 94 | 94 | 85 | 98 |
| Haze degree | ％ | 9.0 | 11.8 | 8.2 | 14.2 |
| Gloss level | ％ | 99 | 101 | 100 | 91 |
Films comprising the polyethylene compositions of inventive examples IE1 and IE2 exhibited a comparable balance of properties to films comprising the polyethylene composition of reference example RE 3. In particular, the SIT of IE1 and IE2 was expected to show significantly higher SIT compared to RE3 containing 1-hexene comonomer. Surprisingly, the SIT of the inventive examples is comparable to the SIT of RE 3. The films comprising the polyethylene compositions of inventive examples IE1 and IE2 exhibited improved properties in terms of impact properties (DDI), sealing properties (SIT and hot tack) and optical properties (haze and gloss) compared to the films comprising the polyethylene composition of comparative example CE 4.
Claims (14)
1. A polyethylene composition comprising a base resin, wherein the base resin comprises
(A) A first ethylene-1-butene copolymer fraction (a) having a 1-butene content of 0.5 to 7.5 wt% based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (a) and a melt flow rate MFR measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg in the range of 1.0 to less than 50.0g/10min 2 The method comprises the steps of carrying out a first treatment on the surface of the And
(B) A second ethylene-1-butene copolymer fraction (B) having a higher 1-butene content than the first ethylene-1-butene copolymer fraction;
wherein the base resin is polymerized in the presence of a single site catalyst system and has a weight of 913.0 to 920.0kg/m 3 And a 1-butene content of 8.0 to 13.0% by weight based on the total weight of monomer units in the base resin,
wherein a 40 μm thick blown film comprising the polyethylene composition has a seal initiation temperature SIT of 90 to 100 ℃.
2. The polyethylene composition according to claim 1, having a melt flow rate MFR, measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg, of 0.7 to 4.0g/10min 2 。
3. The polyethylene composition according to claim 1, having a melt flow rate MFR, measured according to ISO 1133 at a temperature of 190 ℃ and a load of 21.6kg, of 15 to 50g/10min 21 And/or a flow rate ratio FRR of 10 to 30 21/2 The saidFlow rate ratio FRR 21/2 For melt flow rate MFR 21 /MFR 2 Is a ratio of (c).
4. The polyethylene composition according to claim 1, having a polydispersity index PDI of 3 to 8, the polydispersity index PDI being the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn.
5. The polyethylene composition according to claim 1, wherein the weight ratio of the first ethylene-1-butene copolymer (a) to the second ethylene-1-butene copolymer (B) in the base resin is from 35:65 to 47:53.
6. The polyethylene composition of claim 1, wherein the base resin further comprises up to 15 weight percent of a Low Density Polyethylene (LDPE).
7. A process for preparing a polyethylene composition according to any of the preceding claims, comprising the steps of
a) Polymerizing ethylene and 1-butene monomer in a first polymerization reactor in the presence of a single site catalyst system to form a first polymerization mixture comprising a first ethylene-1-butene copolymer fraction (a) having a 1-butene content of 0.5 to 7.5 wt% based on the total weight of monomer units in the first ethylene-1-butene copolymer fraction (a) and a melt flow rate MFR measured according to ISO 1133 at a temperature of 190 ℃ and a load of 2.16kg in the range of 1.0 to less than 50.0g/10min, and the single site catalyst 2 ；
b) Transferring the first polymerization mixture from the first polymerization reactor to a second polymerization reactor;
c) Polymerizing ethylene and 1-butene monomer in the presence of a single site catalyst in the second polymerization reactor to form a second polymerization mixture comprising the first ethylene-1-butene copolymer fraction (a) and a second ethylene-1-butene copolymer fraction (B);
d) Recovering the second polymerization mixture from the second reactor;
e) Forming a powder having a weight of 913.0 to 920.0kg/m 3 A base resin having a 1-butene content of 8.0 to 13.0% by weight based on the total weight of monomer units in the base resin, and
f) The polyethylene composition is prepared.
8. An article comprising the polyethylene composition according to any one of claims 1 to 6.
9. The article of claim 8 which is a film, a blow molded article, or a rotomolded article.
10. The article of claim 8 which is a film having a tear strength in the machine direction TS-MD (N) of at least 0.6N and/or a tear strength in the transverse direction TS-TD (N) of at least 5.0N, measured according to ISO 6383-2:1983 on a 40 μm thick blown film.
11. The article of claim 8 which is a film having a hot tack temperature of 88 to 97 ℃ as measured on a 40 μm thick blown film according to BICM 90720.
12. The article of claim 8 which is a film having a haze of no more than 14.0% as measured according to ASTM D1003 on a 40 μm thick blown film.
13. The article of claim 8 which is a film having a gloss of at least 92.0% measured according to ISO2813 on the inner surface of a 40 μm thick blown film.
14. Use of the polyethylene composition according to any of claims 1 to 6 for the production of an article.
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| EP4108436B1 (en) | 2021-06-24 | 2024-04-17 | Borealis AG | Polyethylene copolymer for a film layer |
| EP4108437B1 (en) | 2021-06-24 | 2024-04-17 | Borealis AG | Polyethylene copolymer with improved sealing performance |
| WO2023155081A1 (en) | 2022-02-17 | 2023-08-24 | Borealis Ag | Flexible laminates with superior sealing performance |
| WO2023198600A1 (en) | 2022-04-11 | 2023-10-19 | Borealis Ag | Copolymer |
| EP4298895A1 (en) | 2022-06-28 | 2024-01-03 | Abu Dhabi Polymers Co. Ltd (Borouge) Llc. | Perforated mulch film and crop cultivation system comprising the same |
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| EP1323746B1 (en) | 2001-12-19 | 2009-02-11 | Borealis Technology Oy | Production of supported olefin polymerisation catalysts |
| EP1323747A1 (en) | 2001-12-19 | 2003-07-02 | Borealis Technology Oy | Production of olefin polymerisation catalysts |
| DE60223926T2 (en) | 2002-10-30 | 2008-11-13 | Borealis Technology Oy | Process and apparatus for the production of olefin polymers |
| EP1462464A1 (en) | 2003-03-25 | 2004-09-29 | Borealis Technology Oy | Metallocene catalysts and preparation of polyolefins therewith |
| US7084247B2 (en) | 2004-03-11 | 2006-08-01 | Peptimmune, Inc. | Identification of self and non-self antigens implicated in autoimmune diseases |
| ES2267026T3 (en) | 2004-04-29 | 2007-03-01 | Borealis Technology Oy | POLYETHYLENE PRODUCTION PROCESS. |
| EP1674490A1 (en) | 2004-12-23 | 2006-06-28 | Borealis Technology Oy | Copolymer |
| EP1739103A1 (en) | 2005-06-30 | 2007-01-03 | Borealis Technology Oy | Catalyst |
| DE602005013376D1 (en) | 2005-08-09 | 2009-04-30 | Borealis Tech Oy | Siloxy substituted metallocene catalysts |
| CN1923861B (en) | 2005-09-02 | 2012-01-18 | 北方技术股份有限公司 | Olefin polymerization method with olefin polymerization catalyst |
| KR101907331B1 (en) | 2014-11-26 | 2018-10-11 | 보레알리스 아게 | Polyethylene composition for a film layer |
| CN108291062B (en) * | 2015-08-05 | 2020-10-27 | 博里利斯股份公司 | Compatible heterophasic polymer blends |
-
2020
- 2020-07-08 CN CN202080052295.0A patent/CN114144440B/en active Active
- 2020-07-08 JP JP2022503785A patent/JP7438324B2/en active Active
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- 2020-07-08 EP EP20737457.0A patent/EP4004066A1/en active Pending
- 2020-07-08 US US17/628,324 patent/US20220282074A1/en active Pending
- 2020-07-08 KR KR1020227005535A patent/KR20220038409A/en not_active Application Discontinuation
- 2020-07-08 WO PCT/EP2020/069282 patent/WO2021013552A1/en active Application Filing
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| JP2022540958A (en) | 2022-09-20 |
| CN114144440A (en) | 2022-03-04 |
| AU2020316600B2 (en) | 2023-11-30 |
| JP7438324B2 (en) | 2024-02-26 |
| EP4004066A1 (en) | 2022-06-01 |
| US20220282074A1 (en) | 2022-09-08 |
| WO2021013552A1 (en) | 2021-01-28 |
| CN116731232A (en) | 2023-09-12 |
| KR20220038409A (en) | 2022-03-28 |
| AU2020316600A1 (en) | 2022-03-10 |
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